Catalyst Compounds and Use Thereof

ABSTRACT

This invention relates to Group 4 catalyst compounds containing anionic bidentate nitrogen/oxygen based ligands catalyst compounds useful for polymerization and or oligomerization of unsaturated monomers. The catalyst compounds are particularly useful, with or without activators, to polymerize olefins, particularly α-olefins, or other unsaturated monomers.

FIELD

This invention relates to catalyst compounds useful for polymerizationand/or oligomerization of unsaturated monomers, such as olefins.

BACKGROUND

As is well known, various processes and catalysts exist for thehomopolymerization or copolymerization of olefins. New polymerizationcatalysts are of interest in the industry because they offer many newopportunities for providing new processes and products to the markets ina cheaper and more efficient manner.

References of general interest related to the instant invention include:WO 2000/020427; WO 2001/010875; WO 2003/054038; Polymer International,2002, 51, 1301-1303; Collection of Czechoslovak Chemical Communications,1988, 63, 371-377; and Transition Metal Chemistry, 1988, 23, 609-613.

There is a need, therefore, for new polymerization technology, catalystsand products produced therefrom that are based on new transition metalcatalyst compounds.

SUMMARY OF THE INVENTION

Group 4 catalyst compounds containing anionic bidentate nitrogen/oxygenbased ligands are provided. The catalyst compounds are useful, with orwithout activators, to polymerize olefins, particularly α-olefins, orother unsaturated monomers. Systems and processes to oligomerize and/orpolymerize one or more unsaturated monomers olefins using the catalystcompound, as well as the oligomers and/or polymers produced therefromare also provided. For the purposes of this disclosure, “α-olefins”includes ethylene.

The catalyst compounds can be represented by the following structure:

wherein M is a Group 4 transition metal (Ti, Zr, or Hf);

N is nitrogen;

O is oxygen;

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 1, 2, or 3;

X may be independently selected from halogen, alkoxide, aryloxide,amide, phosphide, or other anionic ligand when Lewis-acid activators(such as methylalumoxane, aluminum alkyls, alkylaluminum alkoxides) oralkylaluminum halides (capable of donating a hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl or substituted halocarbyl X ligandto the transition metal component) are used, or when an ionic activatoris capable of extracting X, provided that the resulting activatedcatalyst contains at least one M-H or M-C bond into which an olefin caninsert;

each R¹ and R² is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl,preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

n is 1, 2, or 3 such that w+n=4;

additionally in the case where n>1, the ligands (in this case theorganic fragment containing R¹, R², N, and O) may be linked together toform a potentially tetradentate, dianionic ligand;

L is a neutral ligand bonded to M that may include molecules, such asbut not limited to pyridine, acetonitrile, diethyl ether,tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine,trimethylphosphine, triphenylphosphine, lithium chloride, ethylene,propylene, butene, octene, styrene, and the like; and

m is 0, 1, or 2 and indicates the absence or presence of L, providedthat when R² is t-butyl, then R¹ may not be 2,6-dimethylphenyl and X maynot be Cl.

DEFINITIONS

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, and an arrow indicates that the bond maybe dative.

As used herein, the new notation for the Periodic Table Groups is usedas described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

Neutral ligands are defined as ligands that are neutral, with respect tocharge, when formally removed from the metal in their closed shellelectronic state. Neutral ligands contain at least one lone pair ofelectrons, pi-bond or sigma bond that are capable of binding to thetransition metal. Neutral ligands may also be polydentate when more thanone Neutral ligand is connected via a bond or a hydrocarbyl, substitutedhydrocarbyl or a functional group tether. A Neutral ligand may be asubstituent of another metal complex, either the same or different, suchthat multiple complexes are bound together.

Anionic ligands are defined as ligands that are anionic, with respect tocharge, when formally removed from the metal in their closed shellelectronic state. Anionic ligands include hydride, halide, hydrocarbyl,substituted hydrocarbyl or functional group. Non-limiting examples ofanionic ligands include hydride, fluoride, chloride, bromide, iodide,alkyl, aryl, alkenyl, alkynyl, allyl, benzyl, acyl, and trimethylsilyl.Anionic ligands may also be polydentate when more than one anionicligand is connected via a bond or a hydrocarbyl, substituted hydrocarbylor a functional group tether. An anionic ligand may be a substituent ofanother metal complex, either the same or different, such that multiplecomplexes are bound together. A mono-anionic ligand is defined to be ananionic ligand that has a−1 charge. A di-anionic ligand is defined to bean anionic ligand that has a −2 charge.

The terms “hydrocarbyl radical,” “hydrocarbyl” and hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group” and “substituent” are also used interchangeably in thisdocument. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁ to C₁₀₀ radicals, that may be linear, branched, orcyclic, and when cyclic, aromatic or non-aromatic, and includesubstituted hydrocarbyl radicals, halocarbyl radicals, and substitutedhalocarbyl radicals, silylcarbyl radicals, and germylcarbyl radicals asthese terms are defined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃, and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such asO, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂, PbR*₂, andthe like, where R* is independently a hydrocarbyl or halocarbyl radical.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g., F,Cl, Br, I) or halogen-containing group (e.g., CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group, such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at leastone non-carbon atom or group has been inserted within the halocarbylradical such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂,SnR*₂, PbR*₂, and the like where R* is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR*₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like where R* isindependently a hydrocarbyl or halocarbyl radical as defined above andtwo or more R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH₃, GeH₂R*, GeHR*₂, GeR⁵ ₃, GeH₂(OR*),GeH(OR*)₂, Ge(OR*)₃, GeH₂(NR*₂), GeH(NR*₂)₂, Ge(NR*₂)₃, and the likewhere R* is independently a hydrocarbyl or halocarbyl radical as definedabove and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Polar radicals or polar groups are groups in which the heteroatomfunctionality is bonded directly to the indicated atom or atoms. Theyinclude heteroatoms of groups 1-17 of the periodic table either alone orconnected to other elements by covalent or other interactions such asionic, van der Waals forces, or hydrogen bonding. Examples of functionalgroups include carboxylic acid, acid halide, carboxylic ester,carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen(Group 14) analogues, alcohol and phenol, ether, peroxide andhydroperoxide, carboxylic amide, hydrazide and imide, amidine and othernitrogen analogues of amides, nitrile, amine and imine, azo, nitro,other nitrogen compounds, sulfur acids, selenium acids, thiols,sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphoruscompounds, silanes, boranes, borates, alanes, and aluminates. Functionalgroups may also be taken broadly to include organic polymer supports orinorganic support material such as alumina, and silica. Preferredexamples of polar groups include NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂,SbR*₂, SR*, BR*₂, SnR*₃, PbR*₃, and the like where R* is independently ahydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl radical as defined above and two R* may join together to forma substituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also includedare isomers of saturated, partially unsaturated and aromatic cyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, and the like. For this disclosure, when a radical islisted, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl, and alkynyl radicals listed include all isomersincluding where appropriate cyclic isomers, for example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, including, but not limited to ethylene, propylene, and butene,the olefin present in such polymer or copolymer is the polymerized formof the olefin. For example, when a copolymer is said to have an“ethylene” content of 35 wt % to 55 wt %, it is understood that the merunit in the copolymer is derived from ethylene in the polymerizationreaction and said derived units are present at 35 wt % to 55 wt %, basedupon the weight of the copolymer. A “polymer” has two or more of thesame or different mer units. A “homopolymer” is a polymer having merunits that are the same. A “copolymer” is a polymer having two or moremer units that are different from each other. A “terpolymer” is apolymer having three mer units that are different from each other. Theterm “different” as used to refer to mer units indicates that the merunits differ from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An oligomer is typically a polymerhaving a low molecular weight (such an Mn of less than 25,000 g/mol,preferably less than 2,500 g/mol) or a low number of mer units (such as75 mer units or less). An ethylene polymer is an ethylene homopolymerpolymer or a copolymer having more than 50 mol % ethylene, a propylenepolymer is a propylene homopolymer or copolymer having more than 50%propylene, and so on. The terms “catalyst” and “catalyst compound” aredefined to mean a compound capable of initiating catalysis. A catalystcompound may be used by itself to initiate catalysis or may be used incombination with an activator to initiate catalysis. When the catalystcompound is combined with an activator to initiate catalysis, thecatalyst compound is often referred to as a pre-catalyst or catalystprecursor. The term “catalyst system” is defined to mean: 1) a catalystprecursor/activator pair and/or 2) a catalyst compound capable ofinitiating catalysis without an activator. When “catalyst system” isused to describe such a pair before activation, it means the unactivatedcatalyst (pre-catalyst) together with an activator and, optionally, aco-activator. When it is used to describe such a pair after activation,it means the activated catalyst and the activator or othercharge-balancing moiety.

The catalyst compound may be neutral as in a pre-catalyst or a catalystsystem not requiring an activator, or may be a charged species with acounter ion as in an activated catalyst system.

The terms “activator” and “cocatalyst” are used interchangeably herein.A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Insome embodiments, a co-activator can be pre-mixed with the catalystcompound to form an alkylated catalyst compound, also referred to as analkylated invention compound.

DETAILED DESCRIPTION OF THE INVENTION

Group IV dialkyl compounds supported by bidentate amidate ligands areprovided. Such compounds exhibit high activities for the polymerizationof high molecular weight polyethylene. The catalyst compound can berepresented by the following structure:

wherein M is a Group 4 transition metal (Ti, Zr, or Hf);

N is nitrogen;

O is oxygen;

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 1, 2, or 3;

X may be independently selected from halogen, alkoxide, aryloxide,amide, phosphide, or other anionic ligand when Lewis-acid activators(such as methylalumoxane, aluminum alkyls, alkylaluminum alkoxides) oralkylaluminum halides (capable of donating a hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl or substituted halocarbyl X ligandto the transition metal component) are used, or when an ionic activatoris capable of extracting X, provided that the resulting activatedcatalyst contains at least one M-H or M-C bond into which an olefin caninsert;

each R¹ and R² is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl,preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

n is 1, 2, or 3 such that w+n=4;

additionally in the case where n>1, the ligands (in this case theorganic fragment containing R¹, R², N, and O) may be linked together toform a potentially tetradentate, dianionic ligand;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like; and

m is 0, 1, or 2 and indicates the absence or presence of L, providedthat when R² is t-butyl, then R¹ is not 2,6-dimethylphenyl and X may notbe Cl.

Alternately, when R¹ is phenyl or substituted alkyl, then R² is not a C1to C4 alkyl.

Alternately, when R¹ is a substituted phenyl or adamantyl, then R² isnot a C1 to C6 linear or branched alkyl.

Alternately when R² is t-butyl, then R¹ is not dimethyl phenyl and X isnot Cl.

Alternately, when R² is t-butyl, then R¹ is not dimethyl phenyl and X isnot halogen.

Alternately, when R² is t-butyl, then R¹ is not phenyl or substitutedphenyl.

Substituted alkyls are alky groups in which at least one hydrogen atomhas been substituted with at least one functional group such as aheteroatom or NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂,SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at least onenon-hydrocarbon atom or group has been inserted within the alkyl group,such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂,PbR*₂, and the like, where R* is independently hydrogen, a hydrocarbylor halocarbyl radical.

Substituted phenyls are phenyl groups in which at least one hydrogenatom has been substituted with at least one functional group such as aheteroatom or NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂,SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at least onenon-hydrocarbon atom or group has been inserted within the phenyl group,such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂,PbR*₂, and the like, where R* is independently hydrogen, a hydrocarbylor halocarbyl radical.

Specific embodiments of the catalyst compound can include anycombination of the ligands listed in Table 1 below.

TABLE 1 Specific ligand combinations R¹, R² X M L hydrogen chloridetitanium acetonitrile methyl bromide hafnium diethyl ether ethyl iodidezirconium tetrahydrofuran propyl methyl furan butyl ethyl thiofuranpentyl propyl chromane hexyl butyl isochromane heptyl pentylthiochromane octyl hexyl thioisochromane nonyl heptyl quinuclidine decyloctyl benzofuran undecyl nonyl chromene dodecyl decyl isobenzofurantridecyl undecyl isoquinoline tetradecyl dodecyl oxazole octacosyltridecyl phenanthridine nonacosyl tetradecyl pyran triacontyl pentadecylpyridine cyclohexyl hexadecyl quinoline cyclopentyl heptadecylselenophene cycloheptyl octadecyl thiophene cyclooctyl nonadecyltrimethylamine cyclodecyl eicosyl triethylamine cyclododecyl heneicosyltributylamine naphthyl docosyl dimethylaniline phenyl tricosyl trimethylphosphine tolyl tetracosyl triphenyl phosphine benzyl pentacosylethylene phenethyl hexacosyl propylene dimethylphenyl heptacosyl butenediethylphenyl octacosyl hexene anthracenyl nonacosyl octene adamantyltriacontyl cyclohexene norbornyl hydride vinylcyclo hexene CF₃ phenylbenzene NO₂ benzyl styrene t-butyl phenethyl methylstyrene i-propyltolyl naphthyl methoxy fluoride ethoxy trimethylphenyl propoxymethylphenyl butoxy ethylphenyl dimethylamido diethylphenyl diethylamidotriethylphenyl methylethyl amido propylphenyl phenoxy dipropylphenylbenzoxy diisopropyl phenyl allyl tripropylphenyl trimethyl silylmethylisopropylphenyl bis(trimethyl silyl)methyl methylethyl phenyldibutylphenyl butylphenyl pentafluorophenyl

Particularly useful catalyst compounds include whenR¹=2,6-dimethylphenyl, R²=tert-butyl, M=Zr and X=benzyl; whenR¹=2,6-diisopropylphenyl, R²=phenyl, M=Ti and X=chloro; whenR¹=2,6-diisopropylphenyl, R²=pentafluorophenyl, M=Ti and X=chloro; andwhen R¹=2,6-diisopropylphenyl, R²=tert-butyl, M=Ti, and X=dimethylamido.

Activators and Catalyst Activation

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxide,or amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst compound (per metal catalytic site). Theminimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternatepreferred ranges include from 1:1 to 500:1, alternately from 1:1 to200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mol %; alternately the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1.

In a preferred embodiment, the Lewis base modifier is present at a molarratio of X in the Lewis base modifier (as described in the formulaeabove) to aluminum metal in the alumoxane compound (preferablymethylalumoxane) of greater than 1:1, preferably from 1.5:1 to 1000:1,preferably from 2:1 to 500:1, preferably from 2.25:1 to 300:1,preferably from 3:1 to 100:1, preferably from 3.5:1 to 50:1, preferablyfrom 4:1 to 40:1, preferably from 4:1 to 25:1, preferably from 5:1 to20:1, preferably from 5:1 to 15:1, preferably from 5:1 to 10:1. (Forpurposes of calculating the moles of an alkylalumoxane, thealkylalumoxane shall be defined to have an Mw of 43.02 g/mol plus the Mwof the alkyl. For example, methylalumoxane has an Mw of 58.06 g/mol(43.02 g/mol+15.04 g/mol) and ethylalumoxane has an Mw of 72.08 g/mol(43.02+29.06 g/mol) and so on.)

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to a cation or which is only weakly coordinated to acation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible, stabilize the transition metal cation in the sense ofbalancing its ionic charge at +1, and yet retain sufficient lability topermit displacement during polymerization.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups are each independently selected fromalkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides,alkoxy, and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds, and mixtures thereof, preferredare alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and arylgroups having 3 to 20 carbon atoms (including substituted aryls). Morepreferably, the three groups are alkyls having 1 to 4 carbon groups,phenyl, naphthyl, or mixtures thereof. Even more preferably, the threegroups are halogenated, preferably fluorinated, aryl groups. A preferredneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B 1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. patent applicationSer. No. 08/285,380, filed Aug. 3, 1994; all of which are herein fullyincorporated by reference.

Preferred compounds useful as an activator in the process of thisinvention comprise a cation, which is preferably a Bronsted acid capableof donating a proton, and a compatible non-coordinating anion whichanion is relatively large (bulky), capable of stabilizing the activecatalyst species (the Group 4 cation) which is formed when the twocompounds are combined and said anion will be sufficiently labile to bedisplaced by olefinic, diolefinic and acetylenically unsaturatedsubstrates or other neutral Lewis bases, such as ethers, amines, and thelike. Two classes of useful compatible non-coordinating anions have beendisclosed in EP 0 277 003 A1, and EP 0 277 004 A1:1) anioniccoordination complexes comprising a plurality of lipophilic radicalscovalently coordinated to and shielding a central charge-bearing metalor metalloid core and 2) anions comprising a plurality of boron atomssuch as carboranes, metallacarboranes, and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and are preferably represented by thefollowing formula (II):

(Z)_(d) ⁺(A^(d−))  (II)

wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base;H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinatinganion having the charge d-; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe bulky ligand metallocene containing transition metal catalystprecursor, resulting in a cationic transition metal species. Preferably,the activating cation (L-H)_(d) ⁺ is a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

When Z is a reducible Lewis acid it is preferably represented by theformula: (Ar₃C⁺), where Ar is aryl or aryl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl, preferably the reducible Lewis acid is represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl. In a preferred embodiment, the reducible Lewis acid istriphenyl carbenium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6,preferably 3, 4, 5, or 6; n−k=d; M is an element selected from Group 13of the Periodic Table of the Elements, preferably boron or aluminum, andQ is independently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide, and two Q groups may form a ring structure.Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20carbon atoms, more preferably each Q is a fluorinated aryl group, andmost preferably each Q is a pentafluoryl aryl group. Examples ofsuitable A^(d−) components also include diboron compounds as disclosedin U.S. Pat. No. 5,447,895, which is fully incorporated herein byreference.

In a preferred embodiment, this invention relates to a method topolymerize olefins comprising contacting olefins (preferably ethylene)with an amidinate catalyst compound, a chain transfer agent and a boroncontaining NCA activator represented by the formula (14):

Z_(d) ⁺(A^(d−))  (14)

where: Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base(as further described above); H is hydrogen; (L-H) is a Bronsted acid(as further described above); A^(d−) is a boron containingnon-coordinating anion having the charge d (as further described above);d is 1, 2, or 3.

In a preferred embodiment in any NCA's represented by Formula 14described above, the reducible Lewis acid is represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ toC₄₀ hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl, preferably thereducible Lewis acid is represented by the formula: (Ph₃C⁺), where Ph isphenyl or phenyl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl,or a substituted C₁ to C₄₀ hydrocarbyl.

In a preferred embodiment in any of the NCA's represented by Formula 14described above, Z_(d) ⁺ is represented by the formula: (L-H)_(d) ⁺,wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronstedacid; and d is 1, 2, or 3, preferably (L-H)_(d) ⁺ is a Bronsted acidselected from ammoniums, oxoniums, phosphoniums, silyliums, and mixturesthereof.

In a preferred embodiment in any of the NCA's represented by Formula 14described above, the anion component A^(d−) is represented by theformula [M*^(k)*⁺Q*_(n)*]^(d)*⁻ wherein k* is 1, 2, or 3; n* is 1, 2, 3,4, 5, or 6 (preferably 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* isindependently selected from hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbylradicals, said Q* having up to 20 carbon atoms with the proviso that innot more than 1 occurrence is Q* a halide.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as ethylene) with an amidinate catalystcompound, a chain transfer agent and an NCA activator represented by theformula (I):

R_(n)M**(ArNHal)_(4-n)  (I)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula Ialso comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, preferably the cation is Z_(d) ⁺ as described above.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula I described above, R is selected from the groupconsisting of substituted or unsubstituted C₁ to C₃₀ hydrocarbylaliphatic or aromatic groups, where substituted means that at least onehydrogen on a carbon atom is replaced with a hydrocarbyl, halide,halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid,dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl groups; —SR¹, —NR² ₂, and —PR³₂, where each R¹, R², or R³ is independently a substituted orunsubstituted hydrocarbyl as defined above; or a C₁ to C₃₀ hydrocarbylsubstituted organometalloid.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula I described above, the NCA also comprises cationcomprising a reducible Lewis acid represented by the formula: (Ar₃C⁺),where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl, preferably thereducible Lewis acid represented by the formula: (Ph₃C⁺), where Ph isphenyl or phenyl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl,or a substituted C₁ to C₄₀ hydrocarbyl.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by

Formula I described above, the NCA also comprises a cation representedby the formula, (L-H)_(d) ⁺, wherein L is an neutral Lewis base; H ishydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, preferably(L-H)_(d) ⁺ is a Bronsted acid selected from ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879.

Another activator useful herein comprises a salt of a cationic oxidizingagent and a noncoordinating, compatible anion represented by the formula(16):

(OX^(e+))_(d)(A^(d−))_(e)  (16)

wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2, or 3; and A^(d−) is a non-coordinating anionhaving the charge of d- (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Preferred embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

In another embodiment, the amidinate catalyst compounds and CTA'sdescribed herein can be used with Bulky activators. A “Bulky activator”as used herein refers to anionic activators represented by the formula:

where:each R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple ‘Back of theEnvelope’ Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(s), where V_(s) is the scaledvolume. V_(s) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(s) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular Formula of MV Total each Per subst. MV Activator Structure ofboron substituents substituent V_(S) (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl)borate

C₁₀F₇ 34 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 42 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate; triethylammoniumtetrakis(perfluoronaphthyl)borate; tripropylammoniumtetrakis(perfluoronaphthyl)borate; tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate; tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate; N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate; N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate; tropilliumtetrakis(perfluoronaphthyl)borate; triphenylcarbeniumtetrakis(perfluoronaphthyl)borate; triphenylphosphoniumtetrakis(perfluoronaphthyl)borate; triethylsilyliumtetrakis(perfluoronaphthyl)borate; benzene(diazonium)tetrakis(perfluoronaphthyl)borate; trimethylammoniumtetrakis(perfluorobiphenyl)borate; triethylammoniumtetrakis(perfluorobiphenyl)borate; tripropylammoniumtetrakis(perfluorobiphenyl)borate; tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate; tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate; N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate; N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate; tropilliumtetrakis(perfluorobiphenyl)borate; triphenylcarbeniumtetrakis(perfluorobiphenyl)borate; triphenylphosphoniumtetrakis(perfluorobiphenyl)borate; triethylsilyliumtetrakis(perfluorobiphenyl)borate; benzene(diazonium)tetrakis(perfluorobiphenyl)borate; [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B];and the types disclosed in U.S. Pat. No. 7,297,653.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator in the processes of this invention are:

trimethylammonium tetraphenylborate; triethylammonium tetraphenylborate;tripropylammonium tetraphenylborate; tri(n-butyl)ammoniumtetraphenylborate; tri(t-butyl) ammonium tetraphenylborate;N,N-dimethylanilinium tetraphenylborate; N,N-diethylaniliniumtetraphenylborate; N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate; tropillium tetraphenylborate; triphenylcarbeniumtetraphenylborate; triphenylphosphonium tetraphenylboratetriethylsilylium tetraphenylborate; benzene(diazonium)tetraphenylborate;trimethylammonium tetrakis(pentafluorophenyl)borate; triethylammoniumtetrakis(pentafluorophenyl)borate; tripropylammoniumtetrakis(pentafluorophenyl)borate; tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate; tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate; N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate; N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate; tropilliumtetrakis(pentafluorophenyl)borate; triphenylcarbeniumtetrakis(pentafluorophenyl)borate; triphenylphosphoniumtetrakis(pentafluorophenyl)borate; triethylsilyliumtetrakis(pentafluorophenyl)borate; benzene(diazonium)tetrakis(pentafluorophenyl)borate; trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate; dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate; tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate; trimethylammoniumtetrakis(perfluoronaphthyl)borate; triethylammoniumtetrakis(perfluoronaphthyl)borate; tripropylammoniumtetrakis(perfluoronaphthyl)borate; tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate; tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate; N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate; N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate; tropilliumtetrakis(perfluoronaphthyl)borate; triphenylcarbeniumtetrakis(perfluoronaphthyl)borate; triphenylphosphoniumtetrakis(perfluoronaphthyl)borate; triethylsilyliumtetrakis(perfluoronaphthyl)borate; benzene(diazonium)tetrakis(perfluoronaphthyl)borate; trimethylammoniumtetrakis(perfluorobiphenyl)borate; triethylammoniumtetrakis(perfluorobiphenyl)borate; tripropylammoniumtetrakis(perfluorobiphenyl)borate; tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate; tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate; N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate; N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate; tropilliumtetrakis(perfluorobiphenyl)borate; triphenylcarbeniumtetrakis(perfluorobiphenyl)borate; triphenylphosphoniumtetrakis(perfluorobiphenyl)borate; triethylsilyliumtetrakis(perfluorobiphenyl)borate; benzene(diazonium)tetrakis(perfluorobiphenyl)borate; trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; tropilliumtetrakis(3,5-bis (trifluoromethyl)phenyl)borate; triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; and dialkyl ammoniumsalts, such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,and dicyclohexylammonium tetrakis(pentafluorophenyl)borate; andadditional tri-substituted phosphonium salts, such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Preferred activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate; N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate; N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triphenylcarbeniumtetrakis(perfluoronaphthyl)borate; triphenylcarbeniumtetrakis(perfluorobiphenyl)borate; triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triphenylcarbeniumtetrakis(perfluorophenyl)borate; [Ph₃C⁺][B(C₆F₅)₄ ⁻]; [Me₃NH⁺][B(C₆F₅)₄⁻];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate; N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate; trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate; trialkylammoniumtetrakis(perfluoronaphthyl)borate; N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate; trialkylammoniumtetrakis(perfluorobiphenyl)borate; N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate; trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate;N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate; (where alkyl is methyl, ethyl,propyl, n-butyl, sec-butyl, or t-butyl).

In a preferred embodiment, any of the activators described herein may bemixed together before or after combination with the catalyst compoundand/or CTA, preferably before being mixed with the catalyst compoundand/or CTA.

In some embodiments, two NCA activators may be used in thepolymerization and the molar ratio of the first NCA activator to thesecond NCA activator can be any ratio. In some embodiments, the molarratio of the first NCA activator to the second NCA activator is 0.01:1to 10,000:1, preferably 0.1:1 to 1000:1, preferably 1:1 to 100:1.

Further, the typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is a 1:1 molar ratio. Alternate preferredranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1,alternately from 1:1 to 500:1, alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of this invention that the catalystcompounds can be combined with combinations of alumoxanes and NCA's (seefor example, U.S. Pat. Nos. 5,153,157; 5,453,410; European Patent No. EP0 573 120 B1; and PCT Publication Nos. WO 94/07928, and WO 95/14044which discuss the use of an alumoxane in combination with an ionizingactivator).

When an ionic or neutral stoichiometric activator is used, thecatalyst-precursor-to-activator molar ratio is from 1:10 to 1:1; 1:10 to10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to3:1; 1:5 to 5:1; 1:1 to 1:1.2. The catalyst-precursor-to-co-activatormolar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1; 1:100 to 1:1;1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to1:1; 1:2 to 1:1; 1:10 to 2:1.

Preferred activators and activator/co-activator combinations includemethylalumoxane, modified methylalumoxane, mixtures of methylalumoxanewith dimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron, and mixtures of trimethyl aluminum withdimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron.

Scavengers

In some embodiments, scavenging compounds are used with stoichiometricactivators. Typical aluminum or boron alkyl components useful asscavengers are represented by the general formula R^(x)JZ₂ where J isaluminum or boron, R^(x) is as previously defined above, and each Z isindependently R^(x) or a different univalent anionic ligand, such ashalogen (Cl, Br, I), alkoxide (OR^(x)), and the like. Most preferredaluminum alkyls include triethylaluminum, diethylaluminum chloride,tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum,trimethylaluminum, and the like. Preferred boron alkyls includetriethylboron. Scavenging compounds may also be alumoxanes and modifiedalumoxanes including methylalumoxane and modified methylalumoxane.Preferred alkylzinc, aluminum alkyl or organoaluminum compounds whichmay be utilized as scavengers include, for example, trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, and diethyl zinc.

Supported Catalysts

The catalyst compound(s) can be supported or non-supported. To prepareuniform supported catalysts, the catalyst or catalyst precursorpreferably dissolves in the chosen solvent. The term “uniform supportedcatalyst” means that the catalyst, or the catalyst precursor and theactivator, and or the activated catalyst approach uniform distributionupon the support's accessible surface area, including the interior poresurfaces of porous supports. Some embodiments of supported catalystsprefer uniform supported catalysts; other embodiments show no suchpreference.

Invention supported catalyst systems may be prepared by any methodeffective to support other coordination catalyst systems, effectivemeaning that the catalyst so prepared can be used for oligomerizing orpolymerizing olefin in a heterogenous process. The catalyst precursor,activator, co-activator if needed, suitable solvent, and support may beadded in any order or simultaneously.

By one method, the activator, dissolved in an appropriate solvent suchas toluene may be stirred with the support material for 1 minute to 10hours. The total solution volume may be greater than the pore volume ofthe support, but some embodiments limit the total solution volume belowthat needed to form a gel or slurry (about 90% to 400%, preferably about100% to 200% of the pore volume). The mixture is optionally heated from30° C. to 200° C. during this time. The catalyst precursor may be addedto this mixture as a solid, if a suitable solvent is employed in theprevious step, or as a solution. Or alternatively, this mixture can befiltered, and the resulting solid mixed with a catalyst precursorsolution. Similarly, the mixture may be vacuum dried and mixed with acatalyst precursor solution. The resulting catalyst mixture is thenstirred for 1 minute to 10 hours, and the catalyst is either filteredfrom the solution and vacuum dried or evaporation alone removes thesolvent.

Alternatively, the catalyst precursor and activator may be combined insolvent to form a solution. Then the support is added, and the mixtureis stirred for 1 minute to 10 hours. The total solution volume may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 90% to 400%, preferably about 100% to 200% of the pore volume).After stirring, the residual solvent is removed under vacuum, typicallyat ambient temperature and over 10 to 16 hours. But greater or lessertimes and temperatures are possible.

The catalyst precursor may also be supported absent the activator; inthat case, the activator (and co-activator if needed) is added to aslurry process's liquid phase. For example, a solution of catalystprecursor may be mixed with a support material for a period of about 1minute to 10 hours. The resulting pre-catalyst mixture may be filteredfrom the solution and dried under vacuum, or evaporation alone removesthe solvent. The total catalyst-precursor-solution volume may be greaterthan the support's pore volume, but some embodiments limit the totalsolution volume below that needed to form a gel or slurry (about 90% to400%, preferably about 100% to 200% of the pore volume).

Additionally, two or more different catalyst precursors may be placed onthe same support using any of the support methods disclosed above.Likewise, two or more activators or an activator and co-activator may beplaced on the same support.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Any supportmaterial that has an average particle size greater than 10 μm issuitable for use in this invention. Various embodiments select a poroussupport material, such as for example, talc, inorganic oxides, inorganicchlorides; for example, magnesium chloride and resinous supportmaterials, such as polystyrene polyolefin or polymeric compounds or anyother organic support material, and the like. Some embodiments selectinorganic oxide materials as the support material including Group-2, -3,-4, -5, -13, or -14 metal or metalloid oxides. Some embodiments selectthe catalyst support materials to include silica, alumina,silica-alumina, and their mixtures. Other inorganic oxides may serveeither alone or in combination with the silica, alumina, orsilica-alumina. These are magnesia, titania, zirconia, and the like.Lewis acidic materials, such as montmorillonite and similar clays mayalso serve as a support. In this case, the support can optionally doubleas the activator component. But additional activator may also be used.

The support material may be pretreated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents, such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see for example the descriptions in WO 95/15815 andU.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Invention catalyst carriers may have a surface area of from 10-700 m²/g,a pore volume of 0.1 cc/g to 4.0 cc/g and an average particle size of 10μm to 500 μm. Some embodiments select a surface area of 50 m²/g to 500m²/g, a pore volume of 0.5 cc/g to 3.5 cc/g, or an average particle sizeof 20 μm to 200 μm. Other embodiments select a surface area of 100 m²/gto 400 m²/g, a pore volume of 0.8 cc/g to 3.0 cc/g, and an averageparticle size of 30 μm to 100 μm. Invention carriers typically have apore size of 10 to 1000 Angstroms, alternatively 50 to 500 Angstroms, or75 to 350 Angstroms.

Invention catalysts are generally deposited on the support at a loadinglevel of 10 to 100 micromoles of catalyst precursor per gram of solidsupport; alternately 20 to 80 micromoles of catalyst precursor per gramof solid support; or 40 to 60 micromoles of catalyst precursor per gramof support. But greater or lesser values may be used provided that thetotal amount of solid catalyst precursor does not exceed the support'spore volume.

Invention catalysts can be supported for gas-phase, bulk, or slurrypolymerization, or otherwise as needed. Numerous support methods areknown for catalysts in the olefin polymerization art, particularlyalumoxane-activated catalysts; all are suitable for this invention'sbroadest practice. See, for example, U.S. Pat. Nos. 5,057,475 and5,227,440. An example of supported ionic catalysts appears in WO94/03056. U.S. Pat. No. 5,643,847 and WO 96/04319A describe aparticularly effective method. A bulk or slurry process using thisinvention's supported metal complexes activated with alumoxane can beused for ethylene-propylene rubber as described in U.S. Pat. Nos.5,001,205 and 5,229,478. Additionally, those processes suit thisinvention's catalyst systems. Both polymers and inorganic oxides mayserve as supports, as is known in the art. See U.S. Pat. Nos. 5,422,325;5,427,991; 5,498,582; 5,466,649; international publications WO 93/11172and WO 94/07928.

Monomers

The catalyst compounds can be used to polymerize or oligomerize anyunsaturated monomer or monomers. Preferred monomers include C₂ to C₁₀₀olefins, preferably C₂ to C₆₀ olefins, preferably C₂ to C₄₀ olefinspreferably C₂ to C₂₀ olefins, preferably C₂ to C₁₂ olefins. In someembodiments, preferred monomers include linear, branched or cyclicalpha-olefins, preferably C₂ to C₁₀₀ alpha-olefins, preferably C₂ to C₆₀alpha-olefins, preferably C₂ to C₄₀ alpha-olefins, preferably C₂ to C₂₀alpha-olefins, preferably C₂ to C₁₂ alpha-olefins. Preferred olefinmonomers may be one or more of ethylene, propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1,3-methylpentene-1, 3,5,5-trimethylhexene-1, and5-ethylnonene-1.

In another embodiment, the polymer produced herein is a copolymer of oneor more linear or branched C₃ to C₃₀ prochiral alpha-olefins or C₅ toC₃₀ ring containing olefins or combinations thereof capable of beingpolymerized by either stereospecific and non-stereospecific catalysts.Prochiral, as used herein, refers to monomers that favor the formationof isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

Preferred monomers may also include aromatic-group-containing monomerscontaining up to 30 carbon atoms. Suitable aromatic-group-containingmonomers comprise at least one aromatic structure, preferably from oneto three, more preferably a phenyl, indenyl, fluorenyl, or naphthylmoiety. The aromatic-group-containing monomer further comprises at leastone polymerizable double bond such that after polymerization, thearomatic structure will be pendant from the polymer backbone. Thearomatic-group containing monomer may further be substituted with one ormore hydrocarbyl groups including but not limited to C₁ to C₁₀ alkylgroups. Additionally, two adjacent substitutions may be joined to form aring structure. Preferred aromatic-group-containing monomers contain atleast one aromatic structure appended to a polymerizable olefinicmoiety. Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,para-methylstyrene, 4-phenyl-1-butene, and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C₁ to C₁₀ alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,cyclopentadiene, cyclopentene, 4-methylcyclopentene, cyclohexene,4-methylcyclohexene, cyclobutene, vinyladamantane, norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5-butylylnorbornene, 5-pentylnorbomene, 5-hexylnorbornene,5-heptylnorbornene, 5-octylnorbornene, 5-nonylnorbornene,5-decylnorbornene, 5-phenylnorbornene, vinylnorbornene, ethylidenenorbornene, 5,6-dimethylnorbornene, 5,6-dibutylnorbornene, and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least one, typically two, of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). It is furtherpreferred that the diolefin monomers be selected from alpha-omega-dienemonomers (i.e., di-vinyl monomers). More preferably, the diolefinmonomers are linear di-vinyl monomers, most preferably those containingfrom 4 to 30 carbon atoms. Examples of preferred dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, particularly preferreddienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Non-limiting examples of preferred polar unsaturated monomers useful inthis invention, particularly with group 4 and 6 metal compounds, includenitro substituted monomers including 6-nitro-1-hexene; amine substitutedmonomers including N-methylallylamine, N-allylcyclopentylamine, andN-allyl-hexylamine; ketone substituted monomers including methyl vinylketone, ethyl vinyl ketone, and 5-hexen-2-one; aldehyde substitutedmonomers including acrolein, 2,2-dimethyl-4-pentenal, undecylenicaldehyde, and 2,4-dimethyl-2,6-heptadienal; alcohol substituted monomersincluding allyl alcohol, 7-octen-1-ol, 7-octene-1,2-diol,10-undecen-1-ol, 10-undecene-1,2-diol, 2-methyl-3-buten-1-ol; acetal,epoxide and or ether substituted monomers including4-hex-5-enyl-2,2-dimethyl-[1,3]dioxolane,2,2-dimethyl-4-non-8-enyl-[1,3]dioxolane, acrolein dimethyl acetal,butadiene monoxide, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene,1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, allyl glycidyl ether,2,5-dihydrofuran, 2-cyclopenten-1-one ethylene ketal,11-methoxyundec-1-ene, and 8-methoxyoct-1-ene; sulfur containingmonomers including allyl disulfide; acid and ester substituted monomersincluding acrylic acid, vinylacetic acid, 4-pentenoic acid,2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoicacid, 2,6-heptadienoic acid, methyl acrylate, ethyl acrylate, tert-butylacrylate, n-butyl acrylate, methacrylic acid, methyl methacrylate, ethylmethacrylate, tert-butyl methacrylate, n-butyl methacrylate,hydroxypropyl acrylate, acetic acid oct-7-enyl ester, non-8-enoic acidmethyl ester, acetic acid undec-10-enyl ester, dodec-11-enoic acidmethyl ester, propionic acid undec-10-enyl ester, dodec-11-enoic acidethyl ester, and nonylphenoxypolyetheroxy acrylate; siloxy containingmonomers including trimethyloct-7-enyloxy silane, andtrimethylundec-10-enyloxy silane, polar functionalized norbornenemonomers including 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid,cis-5-norbornene-endo-2,3-dicarboxylic acid,5-norbornene-2,2,-dimethanol, cis-5-norbornene-endo-2,3-dicarboxylicanhydride, 5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-methanol,5-norbornene-2-ol, 5-norbornene-2-yl acetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, 2-acetyl-5-norbornene, 7-synmethoxymethyl-5-norbornen-2-one, 5-norbornen-2-ol, and5-norbornen-2-yloxy-trimethylsilane, and partially fluorinated monomersincluding nonafluoro-1-hexene, allyl-1,1,2,2,-tetrafluoroethyl ether,2,2,3,3-tetrafluoro-non-8-enoic acid ethyl ester,1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-oct-7-enyloxy)-ethanesulfonylfluoride, acrylic acid2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-octyl ester, and1,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4-octafluoro-dec-9-enyloxy)-ethanesulfonylfluoride.

In an embodiment herein, the process described herein is used to producean oligomer of any of the monomers listed above. Preferred oligomersinclude oligomers of any C₂ to C₂₀ olefins, preferably C₂ to C₁₂alpha-olefins, most preferably oligomers comprising ethylene, propyleneand or butene are prepared. A preferred feedstock for theoligomerization process is the alpha-olefin, ethylene. But otheralpha-olefins, including but not limited to propylene and 1-butene, mayalso be used alone or combined with ethylene. Preferred alpha-olefinsinclude any C₂ to C₄₀ alpha-olefin, preferably and C₂ to C₂₀alpha-olefin, preferably any C₂ to C₁₂ alpha-olefin, preferablyethylene, propylene, and butene, most preferably ethylene. Dienes may beused in the processes described herein, preferably alpha-omega-dienesare used alone or in combination with mono-alpha olefins.

In a preferred embodiment, the process described herein may be used toproduce homopolymers or copolymers. For the purposes of this inventionand the claims thereto a copolymer may comprise two, three, four or moredifferent monomer units. Preferred polymers produced herein includehomopolymers or copolymers of any of the above monomers. In a preferredembodiment, the polymer is a homopolymer of any C₂ to C₁₂ alpha-olefin.Preferably, the polymer is a homopolymer of ethylene or a homopolymer ofpropylene. In another embodiment, the polymer is a copolymer comprisingethylene and one or more of any of the monomers listed above. In anotherembodiment, the polymer is a copolymer comprising propylene and one ormore of any of the monomers listed above. In another preferredembodiment, the homopolymers or copolymers described, additionallycomprise one or more diolefin comonomers, preferably one or more C₄ toC₄₀ diolefins.

In another preferred embodiment, the polymer produced herein is acopolymer of ethylene and one or more C₃ to C₂₀ linear, branched orcyclic monomers, preferably one or more C₃ to C₁₂ linear, branched orcyclic alpha-olefins. Preferably, the polymer produced herein is acopolymer of ethylene and one or more of propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1,3-methylpentene-1,3,5,5-trimethylhexene-1,cyclopentene, 4-methylcyclopentene, cyclohexene, and4-methylcyclohexene.

In another preferred embodiment, the polymer produced herein is acopolymer of propylene and one or more C₂ or C₄ to C₂₀ linear, branchedor cyclic monomers, preferably one or more C₂ or C₄ to C₁₂ linear,branched or cyclic alpha-olefins. Preferably, the polymer producedherein is a copolymer of propylene and one or more of ethylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1,3-methylpentene-1, and 3,5,5-trimethylhexene-1.

In a preferred embodiment, the polymer produced herein is a homopolymerof norbornene or a copolymer of norbornene and a substituted norbornene,including polar functionalized norbornenes.

In a preferred embodiment, the copolymers described herein comprise atleast 50 mol % of a first monomer and up to 50 mol % of other monomers.

In another embodiment, the polymer comprises a first monomer present atfrom 40 mol % to 95 mol %, preferably 50 mol % to 90 mol %, preferably60 mol % to 80 mol %, and a comonomer present at from 5 mol % to 60 mol%, preferably 10 mol % to 40 mol %, more preferably 20 mol % to 40 mol%, and a termonomer present at from 0 mol % to 10 mol %, more preferablyfrom 0.5 mol % to 5 mol %, more preferably 1 mol % to 3 mol %.

In a preferred embodiment, the first monomer comprises one or more ofany C₃ to C₈ linear branched or cyclic alpha-olefins, includingpropylene, butene, (and all isomers thereof), pentene (and all isomersthereof), hexene (and all isomers thereof), heptene (and all isomersthereof), and octene (and all isomers thereof). Preferred monomersinclude propylene, 1-butene, 1-hexene, 1-octene, cyclopentene,cyclohexene, cyclooctene, hexadiene, cyclohexadiene, and the like.

In a preferred embodiment, the comonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins (provided ethylene, ifpresent, is present at 5 mol % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment, the termonomer comprises one or more of anyC₂ to C₄₀ linear, branched or cyclic alpha-olefins, (provided ethylene,if present, is present at 5 mol % or less), including ethylene,propylene, butene, pentene, hexene, heptene, and octene, nonene, decene,undecene, dodecene, hexadecene, butadiene, hexadiene, heptadiene,pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment, the polymers described above further compriseone or more dienes at up to 10 wt %, preferably at 0.00001 wt % to 1.0wt %, preferably 0.002 wt % to 0.5 wt %, even more preferably 0.003 wt %to 0.2 wt %, based upon the total weight of the composition. In someembodiments, 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments, at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Polymerization Processes

The catalyst compounds can be used to polymerize and/or oligomerize oneor more monomers using any one or more solution, slurry, gas-phase, andhigh-pressure polymerization processes. The catalyst compound andoptional co-catalyst(s), can be delivered as a solution or slurry,either separately to a reactor, activated in-line just prior to areactor, or preactivated and pumped as an activated solution or slurryto a reactor. Polymerizations can be carried out in either singlereactor operations, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operations, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to firstreaction and another component to other reactors. In one preferredembodiment, the pre-catalyst is activated in the reactor in the presenceof olefin.

The catalyst compositions can be used individually or can be mixed withother known polymerization catalysts to prepare polymer blends. Monomerand catalyst selection allows polymer blend preparation under conditionsanalogous to those using individual catalysts. Polymers having increasedMWD for improved processing and other traditional benefits availablefrom polymers made with mixed catalyst systems can thus be achieved.

One or more scavenging compounds can be used. Here, the term scavengingcompound means a compound that removes polar impurities from thereaction environment. These impurities adversely affect catalystactivity and stability. Typically, purifying steps are usually usedbefore introducing reaction components to a reaction vessel. But suchsteps will rarely allow polymerization without using some scavengingcompounds. Normally, the polymerization process will still use at leastsmall amounts of scavenging compounds.

Typically, the scavenging compound will be an organometallic compoundsuch as the Group-13 organometallic compounds of U.S. Pat. Nos.5,153,157; 5,241,025; international publications WO-A-91/09882;WO-A-94/03506; WO-A-93/14132; and that of WO 95/07941. Exemplarycompounds include triethyl aluminum, triethyl borane, tri-iso-butylaluminum, methyl alumoxane, iso-butyl alumoxane, and tri-n-octylaluminum. Those scavenging compounds having bulky or C₆ to C₂₀ linearhydrocarbyl substituents connected to the metal or metalloid centerusually minimize adverse interaction with the active catalyst. Examplesinclude triethylaluminum, but more preferably, bulky compounds, such astri-iso-butyl aluminum, tri-iso-propyl aluminum, and long-chain linearalkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum,tri-n-octyl aluminum, or tri-n-dodecyl aluminum. When alumoxane is usedas the activator, any excess over that needed for activation willscavenge impurities and additional scavenging compounds may beunnecessary. Alumoxanes also may be added in scavenging quantities withother activators, e.g., methylalumoxane, [Me₂HNPh]⁺[B(pfp)₄]⁻ or B(pfp)₃(perfluorophenyl=pfp=C₆F₅).

Gas Phase Polymerization

Generally, in a fluidized gas bed process for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream can be withdrawn from the fluidized bedand recycled back into the reactor. Simultaneously, polymer product canbe withdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See, for example, U.S. Pat. Nos. 4,543,399;4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304;5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are fullyincorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment, when high density polyethylene is desired then the reactortemperature is typically between 70° C. and 105° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the partial pressure of the main monomer. Thepreferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 mol % to 90 mol % and thecomonomer partial pressure is in the range of from about 138 kPa toabout 517 kPa, preferably about 517 kPa to about 2069 kPa, which aretypical conditions in a gas phase polymerization process. Also, in somesystems the presence of comonomer can increase productivity.

In a preferred embodiment, the reactor utilized in the present inventionis capable of producing more than 500 lbs of polymer per hour (227Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher, preferablygreater than 1000 lbs/hr (455 Kg/hr), more preferably greater than10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr(15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr(22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr)to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over100,000 lbs/hr (45,500 Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242; 5,665,818;5,677,375; European publications EP-A-0 794 200; EP-A-0 802 202; andEP-B-634 421; all of which are herein fully incorporated by reference.

In another preferred embodiment, the catalyst system is in liquid formand is introduced into the gas phase reactor into a resin particle leanzone. For information on how to introduce a liquid catalyst system intoa fluidized bed polymerization into a particle lean zone, please seeU.S. Pat. No. 5,693,727, which is incorporated by reference herein.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psig to 735 psig, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process should be operatedabove the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at a pressure of 3620 kPa to 4309 kPa and at a temperature inthe range of about 60° C. to about 104° C., depending on the desiredpolymer melting characteristics. Reaction heat is removed through theloop wall since much of the reactor is in the form of a double-jacketedpipe. The slurry is allowed to exit the reactor at regular intervals orcontinuously to a heated low pressure flash vessel, rotary dryer and anitrogen purge column in sequence for removal of the isobutane diluentand all unreacted monomer and comonomers. The resulting hydrocarbon freepowder is then compounded for use in various applications.

In another embodiment, the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment, the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention, the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention, theconcentration of predominant monomer in the reactor liquid medium is inthe range of from about 1 wt % to about 10 wt %, preferably from about 2wt % to about 7 wt %, more preferably from about 2.5 wt % to about 6 wt%, most preferably from about 3 wt % to about 6 wt %.

Another process of the invention is where the process, preferably aslurry or gas phase process, is operated in the absence of oressentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-iso-butylaluminum, tri-n-hexylaluminum, diethylto aluminum chloride, dibutyl zinc, and the like. This process isdescribed in PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352,which are herein fully incorporated by reference.

In another embodiment, the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-iso-butyl aluminum and anexcess of alumoxane or modified alumoxane.

Homogeneous, Bulk or Solution Phase Polymerization

The catalysts described herein can be used advantageously in homogeneoussolution processes. Generally, this involves polymerization in acontinuous reactor in which the polymer formed and the starting monomerand catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 bar to 3000 bar (10 MPato 30,000 MPa), in which the monomer acts as diluent or in solutionpolymerization using a solvent.

Temperature control in the reactor is obtained by balancing the heat ofpolymerization and with reactor cooling by reactor jackets or coolingcoils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature depends onthe catalyst used. In general, the reactor temperature preferably canvary between about 0° C. and about 160° C., more preferably from about10° C. to about 140° C., and most preferably from about 40° C. to about120° C. In series operation, the second reactor temperature ispreferably higher than the first reactor temperature. In parallelreactor operation, the temperatures of the two reactors are independent.The pressure can vary from about 1 mm Hg to 2500 bar (25,000 MPa),preferably from 0.1 bar to 1600 bar (1 MPa to 16,000 MPa), mostpreferably from 1.0 bar to 500 bar (10 MPa to 5000 MPa).

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor, or plug flow reactor, or more than one reactor operatedin series or parallel. These reactors may have or may not have internalcooling and the monomer feed may or may not be refrigerated. See thegeneral disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See, also, international publications WO 96/33227 and WO97/22639.

Medium and High Pressure Polymerizations

In the high pressure process for the polymerization of ethylene alone orin combination with C₃ to C₁₀ alpha-olefins and optionally othercopolymerizable olefins, the temperature of the medium within which thepolymerization reaction occurs is at least 120° C. and preferably above140° C. and may range to 350° C., but below the decompositiontemperature of said polymer product, typically from 310° C. to 325° C.Preferably, the polymerization is completed at a temperature within therange of 130° C. to 230° C. The polymerization is completed at apressure above 200 bar (20 MPa), and generally at a pressure within therange of 500 bar (50 MPa) to 3500 bar (350 MPa). Preferably, thepolymerization is completed at a pressure within the range from 800 bar(80 MPa) to 2500 bar (250 MPa).

For medium pressure process, the temperature within which thepolymerization reaction occurs is at least 80° C. and ranges from 80° C.to 250° C., preferably from 100° C. to 220° C., and should for a givenpolymer in the reactor, be above the melting point of said polymer so asto maintain the fluidity of the polymer-rich phase. The pressure can bevaried between 100 bar (10 MPa) and 1000 bar (100 MPa) for ethylenehomopolymers and from 30 bar (3 MPa) to 1000 bar (100 MPa), especially50 bar (5 MPa) to 500 bar (50 MPa) for processes producing ethylenecopolymers containing C₃ to C₁₀ olefins and optionally othercopolymerizable olefins.

More recently, polymerization conditions for high pressure and ortemperature polymerizations to prepare propylene homopolymers andcopolymers of propylene with C₃ to C₁₀ olefins and optionally othercopolymerizable olefins have been reported. See U.S. Patent applications60/431,185 filed Dec. 5, 2002; 60/431,077, filed Dec. 5, 2002; and60/412,541, filed Sep. 20, 2002.

After polymerization and deactivation of the catalyst, the polymerproduct can be recovered by processes well known in the art. Any excessreactants may be flashed off from the polymer and the polymer obtainedextruded into water and cut into pellets or other suitable comminutedshapes. For general process conditions, see the general disclosure ofU.S. Pat. Nos. 5,084,534; 5,408,017; 6,127,497; and 6,255,410; which areincorporated herein by reference.

Polymer Product

Preferred polymers produced herein include polyolefins, such as ethylenehomo- or co-polymers or propylene homo- or co-polymers. For example,ethylene copolymers include polymers of ethylene with α-olefins, cyclicolefins and diolefins, vinylaromatic olefins, α-olefinic diolefins,substituted α-olefins, and/or acetylenically unsaturated monomers.Non-limiting examples of α-olefins include propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene,1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene,1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.Non-limiting examples of cyclic olefins and diolefins includecyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane. Non-limiting examples of vinylaromatic olefinsinclude styrene, para-methylstyrene, para-t-butylstyrene,vinylnaphthylene, vinyltoluene, and divinylbenzene. Non-limitingexamples of α-olefinic dienes include 1,4-hexadiene, 1,5-hexadiene,1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene,7-methyl-1,7-octadiene, 1,9-decadiene, 1,11-dodecene, 1,13-tetradeceneand 9-methyl-1,9-decadiene. Likewise propylene copolymers can be madewith the same comonomers. Substituted α-olefins (also called functionalgroup containing α-olefins) include those containing at least onenon-carbon Group 13 to 17 atom bound to a carbon atom of the substitutedα-olefin where such substitution if silicon may be adjacent to thedouble bond or terminal to the double bond, or anywhere in between, andwhere inclusion of non-carbon and non-silicon atoms, such as, forexample, B, O, S, Se, Te, N, P, Ge, Sn, Pb, As, F, Cl, Br, or I, arecontemplated, where such non-carbon or non-silicon moieties aresufficiently far removed from the double bond so as not to interferewith the coordination polymerization reaction with the catalyst and soto retain the generally hydrocarbyl characteristic. By beingsufficiently far removed from the double bond we intend that the numberof carbon atoms, or the number of carbon and silicon atoms, separatingthe double bond and the non-carbon or non-silicon moiety may be 6 orgreater, e.g., 7, or 8, or 9, or 10, or 11, or 12, or 13, or 14 or more.The number of such carbon atoms, or carbon and silicon atoms, is countedfrom immediately adjacent to the double bond to immediately adjacent tothe non-carbon or non-silicon moiety. Examples includeallyltrimethylsilane, divinylsilane, 8,8,8-trifluoro-1-octene,8-methoxyoct-1-ene, 8-methylsulfanyloct-1-ene, 8-dimethylaminooct-1-ene,or combinations thereof. The use of functional group-containingα-olefins where the functional group is closer to the double bond isalso within the scope of embodiments of the invention when such olefinsmay be incorporated in the same manner as are their α-olefin analogs.See, “Metallocene Catalysts and Borane Reagents in The Block/GraftReactions of Polyolefins”, T. C. Chung, et al., Polym. Mater. Sci. Eng.,1995, 73, 463; and the masked α-olefin monomers of U.S. Pat. No.5,153,282. Such monomers permit the preparation of both functional-groupcontaining copolymers capable of subsequent derivatization, and offunctional macromers which may be used as graft and block type polymericsegments. All documents cited herein are incorporated by reference forpurposes of all jurisdictions where such practice is allowed.Copolymerization can also incorporate α-olefinic macromonomers of up to2000 mer units.

In terms of polymer density, the polymers produced herein can range fromabout 0.85 to about 0.95 g/cm³, preferably from about 0.87 to about 0.93g/cm³, more preferably from about 0.89 to about 0.920 g/cm³, (determinedaccording to ASTM D 1505). Polymer molecular weights can range fromabout 50,000 Mn to about 2,000,000 g/mol Mn or greater. Molecular weightdistributions (Mw/Mn) can range from about 1.1 to about 50.0, withmolecular weight distributions from 1.2 to about 5.0 being more typical.Pigments, antioxidants, and other additives, as is known in the art, maybe added to the polymer.

In a preferred embodiment of the invention the polymer produced hereinhas high Mw (e.g. greater than 1,000,000 g/mol), high melting point(such as 130° C. or more) and narrow Mw/Mn (such as less than 3,preferably from greater than 1 to 3).

In another embodiment, this invention relates to:

1. A process for polymerization comprising contacting ethylene andoptionally one or more unsaturated monomers with a catalyst compoundrepresented by the structure:

wherein M is a Group 4 transition metal (Ti, Zr or Hf); N is nitrogen; Ois oxygen; each X is, independently, a hydride, a halogen, ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substitutedhalocarbyl; w is 1, 2, or 3; X is independently selected from halogen,alkoxide, aryloxide, amide, phosphide, or other anionic ligand whenLewis-acid activators (such as methylalumoxane, aluminum alkyls,alkylaluminum alkoxides) or alkylaluminum halides (capable of donating ahydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl X ligand to the transition metal component) are used, or whenan ionic activator is capable of extracting X, provided that theresulting activated catalyst contains at least one M-H or M-C bond intowhich an olefin can insert; each R¹ and R² is, independently, ahydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or asubstituted halocarbyl, preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀substituted halocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ toC₁₀ substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; n is 1, 2, or 3 such that w+n=4; additionallyin the case where n>1, the ligands (in this case the organic fragmentcontaining R¹, R², N, and O) may be linked together to form apotentially tetradentate, dianionic ligand; L is a neutral ligand bondedto M that may include molecules such as but not limited to pyridine,acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, styrene, and thelike; and m is 0, 1, or 2 and indicates the absence or presence of L,provided that when R is ^(t)Butyl then R is not dimethylphenyl, providedthat when R² is t-butyl, then R¹ is not 2,6-dimethyl phenyl and X is notCl.

2. The process according to paragraph 1, wherein M is titanium, or M iszirconium, or M is hafnium.3. The process according to paragraph 1 or 2, wherein X is selected fromthe group consisting of fluoride, chloride, bromide, iodide, methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, hydride, phenyl, benzyl, phenethyl, tolyl,trimethylsilylmethyl, bis(trimethylsilyl)methyl, methoxy, ethoxy,propoxy, butoxy, dimethylamido, diethylamido, methylethylamido, phenoxy,benzoxy, and allyl.4. The process according to paragraph 1 or 2 wherein each X is benzyl,or each X is chloride, or each X is dimethylamido.5. The process according to any of paragraphs 1 to 4, wherein each R¹,R², is, independently, a hydrogen, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, a C₁ to C₃₀ substitutedhalocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, asilyl or another anionic heteroatom-containing group; or independently,may join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure.6. The process according to any of paragraphs 1 to 4 wherein each R¹, R²is, independently, a hydrogen, a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, a C₁ to C₁₀ substitutedhalocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, asilyl or another anionic heteroatom-containing group; or independently,may join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure.7. The process according to any of paragraphs 1 to 6, wherein L isselected from the group consisting of pyridine, acetonitrile, diethylether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine,trimethylphosphine, triphenylphosphine, lithium chloride, ethylene,propylene, butene, octene, and styrene.8. The process according to paragraph 1, wherein: R¹ is2,6-diisopropylphenyl; R² is phenyl; each X is dimethylamido; and m is0.9. The process according to paragraph 1, wherein: R¹ is2,6-dimethylphenyl; R² is phenyl; each X is chloro; and m is 0.10. The process according to paragraph 1, wherein: R¹ is2,6-diisopropylphenyl; R² is phenyl; each X is chloro; and m is 0.11. The process according to paragraph 1, wherein: R¹ is2,6-diisopropylphenyl; R² is pentafluorophenyl; each X is chloro; and mis 0.12. The process according to paragraph 1, wherein: R¹ is2,6-diisopropylphenyl; R² is tert-butyl; each X is dimethylamido; and mis 0.13. The process according to paragraph 1, wherein: R¹ is tert-butyl; R²is phenyl; each X is dimethylamido; and m is 0.14. The process according to paragraph 8, 9, 10, 11, 12 or 13, wherein Mis titanium, zirconium, or hafnium.15. A process for polymerization comprising contacting ethylene andoptionally one or more unsaturated monomers with a catalyst compoundrepresented by any of paragraphs 1 to 14.16. A process for polymerization comprising contacting ethylene andoptionally one or more unsaturated monomers with a catalyst compoundrepresented by the structure:

wherein M is a Group 4 transition metal (Ti, Zr or Hf);

N is nitrogen;

O is oxygen;

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 1, 2 or 3;

X may be independently selected from halogen, alkoxide, aryloxide,amide, phosphide, or other anionic ligand when Lewis-acid activators(such as methylalumoxane, aluminum alkyls, alkylaluminum alkoxides) oralkylaluminum halides (capable of donating a hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl or substituted halocarbyl X ligandto the transition metal component) are used, or when an ionic activatoris capable of extracting X, provided that the resulting activatedcatalyst contains at least one M-H or M-C bond into which an olefin caninsert;

each R¹ and R² is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl,preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

n is 1, 2, or 3 such that w+n=4;

additionally in the case where n>1, the ligands (in this case theorganic fragment containing R¹, R², N, and O) may be linked together toform a potentially tetradentate, dianionic ligand;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like; and

m is 0, 1, or 2 and indicates the absence or presence of L, providedthat when R is ^(t)Butyl then R is not 2,6-dimethylphenyl and X is notCl, provided that when R¹ is phenyl or substituted alkyl, then R² is nota C₁ to C₄ alkyl.17. A process for polymerization comprising contacting ethylene andoptionally one or more unsaturated monomers with a catalyst compoundrepresented by the structure:

wherein M is a Group 4 transition metal (Ti, Zr or Hf);

N is nitrogen;

O is oxygen;

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 1, 2, or 3;

X may be independently selected from halogen, alkoxide, aryloxide,amide, phosphide, or other anionic ligand when Lewis-acid activators(such as methylalumoxane, aluminum alkyls, alkylaluminum alkoxides) oralkylaluminum halides (capable of donating a hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl or substituted halocarbyl X ligandto the transition metal component) are used, or when an ionic activatoris capable of extracting X, provided that the resulting activatedcatalyst contains at least one M-H or M-C bond into which an olefin caninsert;

each R¹ and R² is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl,preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

n is 1, 2, or 3 such that w+n=4;

additionally in the case where n>1, the ligands (in this case theorganic fragment containing R¹, R², N, and O) may be linked together toform a potentially tetradentate, dianionic ligand;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like; and

m is 0, 1, or 2 and indicates the absence or presence of L, providedthat when R is ^(t)Butyl then R is not 2,6-dimethylphenyl and X is notCl, provided that when R¹ is a substituted phenyl or adamantyl, then R²is not a C₁ to C₆ linear or branched alkyl.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. Eighteen illustrative catalystcompounds (shown below), each according to one or more embodimentsdescribed, were used to polymerize ethylene monomer. All catalysts andcatalyst precursors were synthesized according to methods described inthe literature, specifically but not limited to: Arnold et al., Inorg.Chem., 2001, 40, 6069-6072; Schafer et al., Chem. Commun., 2003,2462-2463; Schafer et al., Organic Lett., 2003, 4733-4736; Schafer etal., Can. J. Chem., 2005, 83, 1037-1042; Schafer et al., Inorg. Chem.,2005, 44, 8680-8689; Schafer et al., Angew. Chem. Int. Ed., 2007, 46,354-358; Schafer et al., Eur. J. Inorg. Chem., 2007, 2243-2255; Schaferet al., Organometallics, 2007, 26, 6366-6372. A general route to thecomplexes is outlined below. All reactions were carried out under apurified nitrogen atmosphere using standard glovebox, high vacuum orSchlenk techniques, unless otherwise noted. All solvents used wereanhydrous, de-oxygenated and purified according to known procedures. Allstarting materials were either purchased from Aldrich and purified priorto use or prepared according to procedures known to those skilled in theart.

The syntheses of compounds A through R can be represented as follows:

-   -   1. General Ligand Synthesis:

-   -   2. Synthesis of Dialkyl Derivatives A-E:

-   -   3. Synthesis of Dichloro Derivatives F-J:

-   -   4. Synthesis of Diamido Derivatives K-R:

The bis-amidate metal complexes investigated in this study are detailedbelow:

Bis-Amidate Metal Dialkyls:

Bis-Amidate Metal Dichlorides:

Bis-Amidate Metal Di-Amides:

Polymerization Process:

Ethylene/1-octene copolymerizations were carried out in a parallelpressure reactor, which is described in U.S. Pat. Nos. 6,306,658,6,455,316 and 6,489,168; international publication WO 00/09255; andMurphy et al., J. Am. Chem. Soc., 2003, 125, 4306-4317, each of which isincorporated herein by reference. A pre-weighed glass vial insert anddisposable stirring paddle were fitted to each reaction vessel of thereactor, which contains 48 individual reaction vessels. The reactor wasthen closed and each vessel was individually heated to a set temperature(usually between 50° C. and 100° C.) and pressurized to a pre-determinedpressure of ethylene (generally between 75 psi and 350 psi). 100 uL of1-octene (637 umol) was injected into each reaction vessel through avalve, followed by 500 uL of hexane. 100 uL of tri-n-octylaluminumsolution (10 mmol/L in hexane, 1 umol) was then added to act as aco-catalyst/scavenger. The contents of the vessel were then stirred at800 rpm. An activator solution (usually N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene, 0.40 mmol/L, ˜1 equiv) wasthen injected into the reaction vessel along with 500 uL hexane,followed by a toluene solution of catalyst (dialkyls A-E, 0.40 mmol/L,20-120 nmol) and another aliquot of hexane (500 uL). In the case of thedichlorides F-J and the diamides K-R, the tri-n-octylaluminumscavenger/co-catalyst and activator solutions were replaced with atoluene solution containing 500 equivalents of methylalumoxane ormodified methylalumoxane. In a typical run, reaction conditions werevaried such that two temperatures, three pressures and four catalystconcentrations were investigated. All runs were performed in duplicate.The reaction was then allowed to proceed until a set time limit (usually30 min) or until a set amount of ethylene had been taken up by thereaction (ethylene pressure was maintained in each reaction vessel atthe pre-set level by computer control). At this point, the reaction wasquenched by exposure to air. After the polymerization reaction, theglass vial insert containing the polymer product and solvent was removedfrom the pressure cell and the inert atmosphere glovebox and thevolatile components were removed using a Genevac HT-12 centrifuge andGenevac VC3000D vacuum evaporator operating at elevated temperature andreduced pressure. The vial was then weighed to determine the yield ofthe polymer product. The resultant polymer was analyzed by Rapid GPC(see below) to determine the molecular weight, by FT-IR (see below) todetermine comonomer incorporation, and by DSC (see below) to determinemelting point.

High temperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816;6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409;6,454,947; 6,260,407; and 6,294,388; each of which is incorporatedherein by reference. This apparatus has a series of three 30 cm×7.5 mmlinear columns, each containing PLgel 10 um, Mix B. The GPC system wascalibrated using polystyrene standards ranging from 580 g/mol to3,390,000 g/mol. The system was operated at an eluent flow rate of 2.0mL/min and an oven temperature of 165° C. 1,2,4-trichlorobenzene wasused as the eluent. The polymer samples were dissolved in1,2,4-trichlorobenzene at a concentration of 0.1 mg/mL to 0.9 mg/mL. 250uL of a polymer solution were injected into the system. Theconcentration of the polymer in the eluent was monitored using anevaporative light scattering detector. The molecular weights obtainedare relative to linear polystyrene standards.

Differential Scanning calorimetry (DSC) measurements were performed on aTA-Q100 instrument to determine the melting point of the polymers.Samples were pre-annealed at 220° C. for 15 minutes and then allowed tocool to room temperature overnight. The samples were then heated to 220°C. at a rate of 100° C./min and then cooled at a rate of 50° C./min.Melting points were collected during the heating period.

The ratio of 1-octene to ethylene incorporated in the polymers (weight%) was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+ IRin reflection mode. Samples were prepared in a thin film format byevaporative deposition techniques. Weight % 1-octene was obtained fromthe ratio of peak heights at 1378 and 4322 cm⁻¹. This method wascalibrated using a set of ethylene/1-octene copolymers with a range ofknown wt % 1-octene content.

Polymerization data shown in Table 1 is intended to be representative ofthe catalytic behavior of the catalyst compounds and not comprehensive.

TABLE 1 Selected High Throughput Polymerization Results Activity DSCAmount Temp Pressure Time Yield (g/mmol Mw MWD Tm Example Catalyst(nmol) (° C.) (psi) (sec) (mg) h bar) (kDa) (Mw/Mn) (° C.) 1 A 80 50 751801 10 50  293 1.5 ND 2 A 80 50 200 1801 31 56  307 1.5 128 3 A 80 50350 1801 54 55  811 6.8 131 4 A 80 80 75 1801 46 222  274 2.4 124 5 A 8080 200 1394 90 210  715 9   128 6 A 80 80 350 1007 97 180  876 5.5 131 7B 80 50 200 1800 0 0 ND ND ND 8 B 80 80 200 1800 0 0 ND ND ND 9 C 80 5075 1800 0 0 ND ND ND 10 C 80 50 200 1800 0 0 ND ND ND 11 C 80 50 3501800 1 1 ND ND ND 12 C 80 80 75 1800 1 1 ND ND ND 13 C 80 80 200 1800 35 ND ND ND 14 C 80 80 350 1800 6 8 ND ND ND 15 D 80 50 200 1800 0 0 NDND ND 16 D 80 80 200 1800 0 0 ND ND ND 17 E 80 50 200 1800 0 0 ND ND ND18 E 80 80 200 1800 0 0 ND ND ND 25 F 40 50 75 1800 10 98 2650 2.2 12826 F 40 50 200 1800 23 81 3770 1.7 132 27 F 40 50 350 1800 39 80 39431.7 133 28 F 40 80 75 1800 5 44 ND ND ND 29 F 40 80 200 1800 16 59 20453.4 130 30 F 40 80 350 1800 39 81 3012 2.9 131 31 G 40 50 75 1800 9 88ND ND ND 32 G 40 50 200 1800 32 116 4369 1.7 132 33 G 40 50 350 1800 67138 4242 1.9 132 34 G 40 80 75 1800 4 36 ND ND ND 35 G 40 80 200 1800 1555 2396 5   130 36 G 40 80 350 1800 25 53 3669 3.3 ND 37 H 40 50 75 180016 152 2428 2.2 130 38 H 40 50 200 1800 50 180 3317 2.2 129 39 H 40 50350 593 69 429 3865 2.1 131 40 H 40 80 75 1800 5 47 ND ND ND 41 H 40 80200 1800 21 75 2348 3.2 130 42 H 40 80 350 1800 46 95 3197 2.3 132 43 I40 50 75 1800 2 15 ND ND ND 44 I 40 50 200 1800 5 17 ND ND ND 45 I 40 50350 1800 8 16 ND ND ND 46 I 40 80 75 1800 2 17 ND ND ND 47 I 40 80 2001800 7 24 ND ND ND 48 I 40 80 350 1800 14 30 2196 5.7 ND 49 J 40 50 751800 9 83 ND ND ND 50 J 40 50 200 1800 30 108 3069 1.7 131 51 J 40 50350 1800 59 121 3891 1.3 131 52 J 40 80 75 1800 7 66 ND ND ND 53 J 40 80200 1800 30 107 3373 1.6 130 54 J 40 80 350 1800 115 240 4636 1.3 131 55K 40 50 200 1800 20 74 1555 6.1 135 56 K 40 80 200 1800 18 65 1028 6.7132 57 L 40 50 200 1800 7 25 ND ND ND 58 L 40 80 200 1800 19 69 3358 5.4130 59 M 40 50 200 1800 2 7 ND ND ND 60 M 40 80 200 1800 13 47  82011.4  130 61 N 40 50 200 1800 20 75 3931 1.5 130 62 N 40 80 200 1800 54213 3532 1.6 130 63 O 40 50 200 1800 3 9 ND ND ND 64 O 40 80 200 1800 1037  932 12.9  132 65 P 40 50 200 1660 20 71 3540 3.2 131 66 P 40 80 2001503 35 127 3029 4.5 129 67 Q 40 50 200 1800 12 42 2477 2.3 134 68 Q 4080 200 1800 14 52  932 5   130 69 R 40 50 200 1800 10 35 ND ND ND 70 R40 80 200 1800 19 68  448 2.9 131 ND = not determined

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related applications, and/or testing proceduresto the extent they are not inconsistent with this text, provided howeverthat any priority document not named in the initially filed applicationor filing documents is NOT incorporated by reference herein. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A process for polymerization comprisingcontacting ethylene and optionally one or more unsaturated monomers witha catalyst compound represented by the structure:

wherein M is a Group 4 transition metal (Ti, Zr or Hf); N is nitrogen; Ois oxygen; each X is, independently, a hydride, a halogen, ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substitutedhalocarbyl; w is 1, 2, or 3; X may be independently selected fromhalogen, alkoxide, aryloxide, amide, phosphide, or other anionic ligandwhen Lewis-acid activators (such as methylalumoxane, aluminum alkyls,alkylaluminum alkoxides) or alkylaluminum halides (capable of donating ahydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl X ligand to the transition metal component) are used, or whenan ionic activator is capable of extracting X, provided that theresulting activated catalyst contains at least one M-H or M-C bond intowhich an olefin can insert; each R¹ and R² is, independently, ahydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or asubstituted halocarbyl, preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀substituted halocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ toC₁₀ substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; n is 1, 2, or 3 such that w+n=4; additionallyin the case where n>1, the ligands (in this case the organic fragmentcontaining R¹, R², N, and O) may be linked together to form apotentially tetradentate, dianionic ligand; L is a neutral ligand bondedto M that may include molecules such as but not limited to pyridine,acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, styrene, and thelike; and m is 0, 1, or 2 and indicates the absence or presence of L,provided that when R is ^(t)Butyl then R is not dimethylphenyl, providedthat when R² is t-butyl, then R¹ is not 2,6-dimethyl phenyl and X is notCl.
 2. The process according to claim 1, wherein M is titanium.
 3. Theprocess according to claim 1, wherein M is zirconium.
 4. The processaccording to claim 1, wherein M is hafnium.
 5. The process according toclaim 1, wherein X is selected from the group consisting of fluoride,chloride, bromide, iodide, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl,phenethyl, tolyl, trimethylsilylmethyl, bis(trimethylsilyl)methyl,methoxy, ethoxy, propoxy, butoxy, dimethylamido, diethylamido,methylethylamido, phenoxy, benzoxy, and allyl.
 6. The process accordingto claim 1, wherein each X is benzyl.
 7. The process according to claim1, wherein each X is chloride.
 8. The process according to claim 1,wherein each X is dimethylamido.
 9. The process according to claim 1,wherein each R¹, R², is, independently, a hydrogen, a C₁ to C₃₀hydrocarbyl, a C₁ to C₃₀ substituted hydrocarbyl, a C₁ to C₃₀halocarbyl, a C₁ to C₃₀ substituted halocarbyl, a halogen, an alkoxide,a sulfide, an amide, a phosphide, a silyl or another anionicheteroatom-containing group; or independently, may join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure.
 10. The processaccording to claim 1, wherein each R¹, R² is, independently, a hydrogen,a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀ substituted hydrocarbyl, a C₁ toC₁₀ halocarbyl, a C₁ to C₁₀ substituted halocarbyl, a halogen, analkoxide, a sulfide, an amide, a phosphide, a silyl or another anionicheteroatom-containing group; or independently, may join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure.
 11. The processaccording to claim 1, wherein L is selected from the group consisting ofpyridine, acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, and styrene. 12.The process according to claim 1, wherein: R¹ is 2,6-diisopropylphenyl;R² is phenyl; each X is dimethylamido; and m is
 0. 13. The processaccording to claim 12, wherein M is titanium.
 14. The process accordingto claim 12, wherein M is zirconium.
 15. The process according to claim12, wherein M is hafnium.
 16. The process according to claim 1, wherein:R¹ is 2,6-dimethylphenyl; R² is phenyl; each X is chloro; and m is 0.17. The process according to claim 16, wherein M is titanium.
 18. Theprocess according to claim 16, wherein M is zirconium.
 19. The processaccording to claim 17, wherein M is hafnium.
 20. The process accordingto claim 1, wherein: R¹ is 2,6-diisopropylphenyl; R² is phenyl; each Xis chloro; and m is
 0. 21. The process according to claim 20, wherein Mis titanium.
 22. The process according to claim 20, wherein M iszirconium.
 23. The process according to claim 20, wherein M is hafnium.24. The process according to claim 1, wherein: R¹ is2,6-diisopropylphenyl; R² is pentafluorophenyl; each X is chloro; and mis
 0. 25. The process according to claim 24, wherein M is titanium. 26.The process according to claim 24, wherein M is zirconium.
 27. Theprocess according to claim 24, wherein M is hafnium.
 28. The processaccording to claim 1, wherein: R¹ is 2,6-diisopropylphenyl; R² istert-butyl; each X is dimethylamido; and m is
 0. 29. The processaccording to claim 28, wherein M is titanium.
 30. The process accordingto claim 28, wherein M is zirconium.
 31. The process according to claim28, wherein M is hafnium.
 32. The process according to claim 1, wherein:R¹ is tert-butyl; R² is phenyl; each X is dimethylamido; and m is
 0. 33.The process according to claim 32, wherein M is titanium.
 34. Theprocess according to claim 32, wherein M is zirconium.
 35. The processaccording to claim 32, wherein M is hafnium.
 36. A process forpolymerization comprising contacting ethylene and optionally one or moreunsaturated monomers with a catalyst compound represented by thestructure:

wherein M is a Group 4 transition metal (Ti, Zr or Hf); N is nitrogen; Ois oxygen; each X is, independently, a hydride, a halogen, ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substitutedhalocarbyl; w is 1, 2 or 3; X may be independently selected fromhalogen, alkoxide, aryloxide, amide, phosphide, or other anionic ligandwhen Lewis-acid activators (such as methylalumoxane, aluminum alkyls,alkylaluminum alkoxides) or alkylaluminum halides (capable of donating ahydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl X ligand to the transition metal component) are used, or whenan ionic activator is capable of extracting X, provided that theresulting activated catalyst contains at least one M-H or M-C bond intowhich an olefin can insert; each R¹ and R² is, independently, ahydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or asubstituted halocarbyl, preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀substituted halocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ toC₁₀ substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; n is 1, 2, or 3 such that w+n=4; additionallyin the case where n>1, the ligands (in this case the organic fragmentcontaining R¹, R², N, and O) may be linked together to form apotentially tetradentate, dianionic ligand; L is a neutral ligand bondedto M that may include molecules such as but not limited to pyridine,acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, styrene, and thelike; and m is 0, 1, or 2 and indicates the absence or presence of L,provided that when R is ^(t)Butyl then R is not 2,6-dimethylphenyl and Xis not Cl, provided that when R¹ is phenyl or substituted alkyl, then R²is not a C₁ to C₄ alkyl.
 37. A process for polymerization comprisingcontacting ethylene and optionally one or more unsaturated monomers witha catalyst compound represented by the structure:

wherein M is a Group 4 transition metal (Ti, Zr or Hf); N is nitrogen; Ois oxygen; each X is, independently, a hydride, a halogen, ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substitutedhalocarbyl; w is 1, 2, or 3; X may be independently selected fromhalogen, alkoxide, aryloxide, amide, phosphide, or other anionic ligandwhen Lewis-acid activators (such as methylalumoxane, aluminum alkyls,alkylaluminum alkoxides) or alkylaluminum halides (capable of donating ahydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl X ligand to the transition metal component) are used, or whenan ionic activator is capable of extracting X, provided that theresulting activated catalyst contains at least one M-H or M-C bond intowhich an olefin can insert; each R¹ and R² is, independently, ahydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or asubstituted halocarbyl, preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀substituted hydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀substituted halocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ toC₁₀ substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; n is 1, 2, or 3 such that w+n=4; additionallyin the case where n>1, the ligands (in this case the organic fragmentcontaining R¹, R², N, and O) may be linked together to form apotentially tetradentate, dianionic ligand; L is a neutral ligand bondedto M that may include molecules such as but not limited to pyridine,acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, styrene, and thelike; and m is 0, 1, or 2 and indicates the absence or presence of L,provided that when R is ^(t)Butyl then R is not 2,6-dimethylphenyl and Xis not C₁, provided that when R¹ is a substituted phenyl or adamantyl,then R² is not a C₁ to C₆ linear or branched alkyl.